Ethylene bromide iodide

R. T. Dillon (1932) studied the reaetion between ethylene bromide and potassium iodide in 99% methanol with the following data ... 

Ethyl benzene Ethyl bromide 2-Ethyl butyl acrylate Ethyl chloride Ethyl ether Ethyl formate 2-Ethyl hexyl acrylate Ethyl iodide Ethyl propionate Ethyl propyl ether Ethyl sulfide Ethylene bromide Ethylene chloride Ethylene glycol Ethylidebe chloride Fluorobenzene Formic acid Freon-11 Freon-12 Freon-21 Freon-22 Freon-113 Glycerol, 100%... 

The reaction between ethylene bromide and potassium iodide in 99% methanol (inert) has been found to be first-order with respect to each reactant (second-order overall) (Dillon, 1932). The reaction can be represented by C2liiBr2 + 3K1 —> C2H4 + 2KBr + KI3 or A + 3B - products. 

NOTE Typical agents of concern are hydrogen sulfide, amines, chlorides, bromides, iodides, cyanides, fluorides, naphthenic acid and polythionic acid. Other agents affecting elastomer selection include ketones, ethylene oxide, sodium hydroxide, methanol, benzene and solvents. 

The high chemoselectivity of organozinc reagents also allowed the use of the functionalized secondary a-acetoxy alkyl bromide 50 which was converted to 34a (equation 19)36, a product previously obtained by the cyclization of a 5-ethylenic primary iodide bearing the acetoxy group at the allylic position (equation 13). 

The following qualitative observations on the action of liquid ammonia on organic compounds are mainly by E. C. Franklin and C. A. Kraus, those in brackets are by G. Gore. Aliphatic compounds.—Halides methyl iodide, m. chloroform, reacts, and m. bromoform, m. iodoform, v.s., ethyl bromide and iodide, s. ethylene bromide, s. ethylidene chloride, m. isobutyl bromide, s. amyl bromide, s.s. tribromomethane, v.s. nitrotriohloromethane, m. perehloroethane (n.s.) perchloroethylene (m.) dichloroacetylene (s.). Alcohols methyl, m. ethyl, m. propyl, m. normal butyl,... 

Ethoxyethyl bromide has been prepared by the action of sodium ethoxide upon ethylene bromide s by the action of bromine upon /3-ethoxyethyl iodide and by the procedure adopted here, which was first used by Chalmers.4 The action of sodium bromide and sulfuric acid on /3-ethoxyethyl alcohol cleaves the ether linkage. 

Therefore, in accordance with the facts, viz., (a) unsaturation and instability of ethylene, (b) The formation of ethylene from ethyl alcohol by loss of water, (c) The formation of ethylene from ethyl bromide, or iodide, by loss of hydrogen bromide, or iodide, (d) The identity of the di-brom addition product of ethylene ethylene bromide), with the symmetrical di-brom ethane and, (e) in accordance with our conceptions of carbon in its space relations and the geometric condition of such space arrangement, the structural formula for ethylene has been accepted as follows ... 

Reactions between dimethyl sulfate and lH-2,l,3-benzothiadiaz.ine 1,1-dioxide (27) and its derivatives have been reported (62JA1994 78JHC1521) (Scheme 3). With methylene iodide, 27 affords the dimer product 32, but with ethylene bromide, 1,3-dibromopropane, and a,a -dibromo-o-xylene, 1,3-bridged derivatives 33, 34, and 35 are obtained (71M1055 71 Ml583). 

The dimerization of ethylene into n-butenes by means of tetrachlo-robis(ethylene)palladium in nonhydroxylic media (benzene or dioxane) has been attempted [246]. Other palladium salts (fluoride, bromide, iodide, nitrate) tested in the dimerization of olefins do not form complexes of the type (C2H4),Pd2X4. Palladium cyanide dimerizes ethylene twice as slowly as PdCL, probably on account of deactivation of the catalyst by a polyethylene deposit formed along with the dimer. 

The reactivity is further influenced by the branching of the carbon chain and by the possible presence of a double bond and position of a second halogen atom. Among the tested monovalent and divalent halo compounds (5), methyl iodide, allyl bromide, benzyl bromide, and methylene iodide were found most reactive, a medium reactivity was observed for penta-methylene bromide, ethyl bromide, w-propyl bromide, n-butyl bromide, and w-amyl bromide, while ethylene bromide and isobutyl bromide reacted most slowly. 

Methyl iodide, ethyl bromide and ethyl iodide also evolve small amounts of ethylene when treated as above. If this is suspected, a small quantity of the substance should be heated with alcoholic NaOH solution in a small flask, fitted with a knee delivery-tube. Pass the gas evolved through a very dilute solution of KMn04 which has been made alkaline with aqueous NagCOj solution. If ethylene has been formed, a brown precipitate of MnOj will be produced (a transient green colour may appear). 

With Unsaturated Compounds. The reaction of unsaturated organic compounds with carbon monoxide and molecules containing an active hydrogen atom leads to a variety of interesting organic products. The hydroformylation reaction is the most important member of this class of reactions. When the hydroformylation reaction of ethylene takes place in an aqueous medium, diethyl ketone [96-22-0] is obtained as the principal product instead of propionaldehyde [123-38-6] (59). Ethylene, carbon monoxide, and water also yield propionic acid [79-09-4] under mild conditions (448—468 K and 3—7 MPa or 30—70 atm) using cobalt or rhodium catalysts containing bromide or iodide (60,61). 

Acetoxyandrost-5-en-17-one (59) is converted into the ethylene ketal (60) by treatment with ethylene glycol, triethylorthoformate and p-toluenesulfonic acid. The ketal is brominated with pyridinium bromide perbromide in THF and then treated with sodium iodide to remove bromine from the 5 and 6 positions. This gives the 16a-bromo compound (61) which is hydrolyzed in methanol to the free alcohol (62). Dehydrobromination is effected with potassium Fbutoxide in DMSO to give the -compound (63). Acid catalyzed hydrolysis of the ketal in aqueous acetone gives the title compound (64). ... 

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